The porous hybrid inorganic-organic materials that are explained in this invention are defined as inorganic-organic coordination polymers composed of central metallic ions and organic ligands coordinated to the metal ions. The porous hybrid inorganic-organic materials are crystalline materials having porous structures with the pore sizes of molecules or nanometers, and the framework structures of porous hybrid inorganic-organic materials are composed of both organic materials and inorganic species. The porous hybrid inorganic-organic material is wide terminology and also can be called as porous coordination polymer (Angew. Chem. Intl. Ed., 43, 2334. 2004) or metal-organic framework (Chem. Soc. Rev., 32, 276, 2003). The studies on these materials have been recently developed by the combination of coordination chemistry and materials science. These materials are widely studied because they have many applications such as adsorbents, gas storages, sensors, membranes, functional thin films, catalysts and catalyst supports due to high surface area and pores of size of molecules or nanometers. Moreover, they can be used to encapsulate molecules or separate molecules depending on the sizes of molecules. These porous hybrid inorganic-organic materials can be synthesized by several methods including solvent-diffusion method, hydrothermal synthesis using water as solvent and a solvothermal synthesis using an organic solvent (Microporous Mesoporous Mater., 73, 15, 2004; Accounts of Chemical Research, 38, 217, 2005).
The synthesis of porous hybrid inorganic-organic materials can be executed, similar to the synthesis of inorganic porous materials including zeolites and mesoporous materials, under autogenous pressure in the presence of water or suitable solvents at zeolites and mesoporous materials, during several days at high temperature after loading reactants in a high pressure reactor such as an autoclave. The heat source for high temperature has generally been electric or resistive heating. For example, an autoclave containing precursors including metal salts, organic ligands and water or solvent was heated using an electric heater or an electric oven at a constant temperature. However, the methods of the previous embodiments have drawbacks of using excessive energy because the nucleation or crystallization is very slow. Moreover, the methods are very inefficient because the synthesis can be carried out only by batch reactions (Accounts of Chemical Research, 38, 217, 2005). The previous synthesis methods are considered as inefficient methods to implement commercial applications because of high production cost.
Moreover, it is known that porous catalytic materials with small particle size have advantages of increased activity and facile regeneration of used catalysts because diffusivity increases with decreasing the crystal size of catalysts (Catalysis Today, 41, 37, 1998; Polymer Degradation and Stability 70, 365, 2000). Moreover, nanocrystalline porous materials have many applications in the fields of sensors, opto-electronics and medicines (Chem. Mater., 17, 2494, 2005). However, it is not easy to synthesize small crystals, and so-called nanoparticles smaller than 100 nm is especially difficult to obtain because of easy aggregation or coagulation. Carbon or polymer templates may be used to synthesize nanoparticles even though the synthesis process is complex. However, it is not easy to obtain pure nanoparticles without a template because small particles grow easily to a big size when the template is removed.
Moreover, it is necessary to prepare porous hybrid inorganic-organic materials with homogeneous particle size and membrane or thin film of the materials for the applications in sensors or opto-electronic devices. In a previous method, membranes or thin films were made by two steps of synthesizing and making a simple composite by impregnation of porous hybrid inorganic-organic materials on a polymer. However, the process is complex and it is difficult to apply for insoluble porous hybrid inorganic-organic materials. Another method using a gold plate on which an organic functional group is anchored is reported; however, the method is complicated due to the anchoring and recrystallization (Journal of the American Chemical Society, 127, 13744, 2005).
Hence, it is an object of the present invention to provide a new preparation method of a porous hybrid inorganic-organic material and, especially nanocrystalline porous hybrid inorganic-organic material including thin film or membrane.
On the other hand, there have been mass production methods such as hydrothermal crystallization for inorganic porous materials including zeolites because they have been used for 50 years or so in the petrochemistry or refinery. However, the general hydrothermal method using electric heating is ineffective due to long crystallization time. Therefore, since 1988, microwave heating has been suggested to increase the efficiency or productivity in the synthesis of inorganic porous materials (U.S. Pat. No. 4,778,666; Catal. Survey Asia, 8, 91, 2004). It was reported that synthesis time could be decreased by using microwave heating compared with conventional electric heating, and continuous synthesis was also reported for a few cases using microwave heating. However, the synthesis mechanisms of porous hybrid inorganic-organic materials are very different to that of inorganic porous materials. Organic molecules do not remain or incorporated in an inorganic porous material because organic molecules are removed by calcination after synthesis even though some organic amines or ammonium salts are used as templating molecules in the synthesis of inorganic porous materials. On the other hands, organic molecules construct a framework structure of porous hybrid inorganic-organic materials. In aminorganic porous material, oxygen atoms link a metal and another metal, whereas ligand, derived from an organic molecule, connects metal species. Therefore, the synthesis of porous hybrid inorganic-organic materials has been accomplished by using electric heating only because the synthesis is just at the beginning stage of development (Science, 2005, 309, 2040). Therefore, there have been few attemptsto synthesize a porous hybrid inorganic-organic material by using microwave heating.
Recently, the synthesis of porous hybrid inorganic-organic materials by using microwave irradiation, after adequatepretrements, has been reported by the present inventors (Kor. Pat. Application 2005-0045153); however, there has been no report on the crystal size control or the synthesis of nanocrystalline porous hybrid inorganic-organic materials.
Moreover, to synthesize nanocrystalline porous hybrid inorganic-organic materials, preferably in a short reaction time, and more preferably in a continuous reaction mode, is very important for commercial applications of porous hybrid inorganic-organic materials in catalysts, catalyst supports, adsorbents, ion exchangers, magnetic materials, thin films, gas storages, nanoreactors and nanosciences such as storage, preparation and separation of nanomaterials.